Title
Theoretical studies of the gas-phase pyrolysis kinetics of ω-bromonitriles, ZCH<inf>2</inf>CH<inf>2</inf>Br [Z = NC, NCCH <inf>2</inf>, NCCH<inf>2</inf>CH<inf>2</inf>]
Date Issued
01 March 2009
Access level
metadata only access
Resource Type
research article
Author(s)
Abstract
The gas-phase elimination of several ω-bromonitriles (ZCH 2CH2Br, Z = NC, NCCH2, NCCH2CH 2) has been examined at the MP2/6-31G(d,p), MP2/6-31G(2d,2p), B3PW91/6-31G(2d,2p), and MPW91PW91/6-31(2p,2d) levels of theory. The bromonitriles yield the corresponding cyano-olefin and HBr gas in a rate-determining step. The MPW91PW91/6-31G(2p,2d) results suggest a concerted mechanism, with a polar, four-membered transition state. The calculated kinetic and thermodynamic parameters were found to be within reasonable agreement with the experimental determinations. Substituent effects are discussed in terms of electronic structure. © 2008 Wiley Periodicals, Inc.
Start page
168
End page
175
Volume
41
Issue
3
Language
English
OCDE Knowledge area
Física atómica, molecular y química
Subjects
Scopus EID
2-s2.0-61649118985
Source
International Journal of Chemical Kinetics
ISSN of the container
05388066
Sources of information:
Directorio de Producción Científica
Scopus